利用Picarro测试石笋包裹体水氢, 氧同位素的方法

A speleothem fluid inclusion extraction and isotope analysis system was established based on a vacuum extraction device and a Picarro L2140-i wavelength scanned cavity ring-down spectroscopy (WS-CRDS) water isotope analyzer. WS-CRDS allows to measure the stable oxygen and hydrogen isotope composition (δ¹⁸O and δD) of small water samples simultaneously, which is faster, simpler, and requires less maintenance compared to currently used continuous-flow isotope ratio mass spectrometry (CF-IRMS). The precision of water isotopic analysis utilizing the WS-CRDS is often superior to that of CF-IRMS. Therefore, the use of Picarro for isotope analysis has rapidly gained popularity. The oxygen isotopic composition of speleothem calcite (δ¹⁸O_c) is one of the main proxies of speleothem-based paleoclimate reconstructions, but the interpretation of δ¹⁸O_c remains complex as it can be influenced by many factors. Speleothem fluid inclusions contain the characteristics of cave drip water. The δ¹⁸O and δD values of fluid inclusion water provide direct information about paleoprecipitation, and can be further used to reconstruct paleotemperature when combined with δ¹⁸O_c. The present paper contains a detailed description of the system as we have designed it, and provides an introduction to the system's performance. The vacuum extraction device, connected to the Picarro analyzer, is designed to release the water trapped in speleothem fluid inclusions by pneumatically-operated crushing of discrete speleothem calcite chips. The whole device is kept at a temperature of 120°C to ensure the total and instantaneous vaporization of the water without isotopic fractionation. The vaporized water is carried by a flow of high-purity nitrogen to a 40 mL volume for homogenization, and is then introduced into the Picarro analyzer for δ¹⁸O and δD analysis. A syringe injection unit was added to the vacuum extraction device to be able to measure standard water, with δ¹⁸O and δD values similar to the speleothem samples, before and during measurements. To verify the precision and accuracy of the system, the same standard water samples were measured with an automated Picarro L2140-i set-up that includes an autosampler and a Picarro evaporation unit. The δ¹⁸O and δD values of standard waters as measured by both systems are comparable. Using the crushing device, speleothem samples from the East Asian Monsoon region yield paired δ¹⁸O/δD values within ±0.5‰ of the Global Meteoric Water Line (GMWL), indicating no isotopic fractionation during the measurements. The precision is a function of the water amount released and of the isotopic composition of the sample. The reproducibility of crushed speleothem samples, whose water vapor concentration is between 2500 and 50000 ppm, is 0.5‰ for δ¹⁸O and 2‰ for δD (1 SD), similar to results obtained from other published measuring systems.